Infrared Photodissociation Spectroscopy Research Articles

A Coppoborylene Stabilized by Multicenter Covalent Bonding and Its Amphoteric Reactivity to CO

A cationic copper‐stabilized coppoborylene was prepared and structurally characterized via infrared photodissociation spectroscopy and density functional theory calculations. This structure exemplifies a new class of borylenes stabilized by three‐center‐two‐electron metal‐boron‐metal covalent bonding interaction, displaying exceptional σ‐acidity and unparalleled π‐donor capability for CO activation that outperforms all of the known transition metal cations and is comparable or even superior to the documented base‐trapped borylenes. Its neutral form represents a monovalent boron compound with a strongly reactive amphoteric boron center built on transition‐metal‐boron bonds, which inspires the design and synthesis of new members of the borylene family.

Exploring structures of small anionic nickel-ethanol clusters with infrared spectroscopy.

Small anionic nickel clusters with ethanol are investigated with a combination of mass-selective infrared photodissociation spectroscopy in a molecular beam and density functional theory simulations at the BLYP/6-311g(d,p) and TPSSh/def2-TZVPP level. In this context, the O-H stretching vibration of the ethanol is analyzed to obtain information about the structural motif, the geometry of the metal core, and the spin state of the clusters. For the [Ni2(EtOH)]- and [Ni3(EtOH)]- clusters, we assign quartet states of motifs with a hydrogen bond from the ethanol to the linear nickel core. The aggregation of a further ethanol molecule, yielding the [Ni3(EtOH)2]- cluster, results in the formation of a cooperative hydrogen bond network between the nickel core and the two ethanol molecules.

Infrared Photodissociation Spectroscopy of Water-Tagged Ions with a Widely Tunable Quantum Cascade Laser for Planetary Science Applications.

This work presents a benchtop method for collecting the room temperature gas phase infrared (IR) action spectra of protonated amino acids and their isomers. The adopted setup uses a minimally modified commercial electrospray ionization linear ion trap mass spectrometer (ESI-LIT-MS) coupled to a broadband continuous wave (cw) quantum cascade laser (QCL) source. This approach leverages messenger assisted action spectroscopic techniques using water-tagged molecular ions with complex formation, irradiation, and subsequent analysis, all taking place within a single linear ion trap stage. This configuration thus circumvents the use of multiple mass selection and analysis stages, cryogenic buffer cells, and complex high-power laser systems typically called upon to execute these techniques. The benchtop action spectrometer is used to collect the 935-1600 cm-1 (6.2-10.7 μm) IR action spectrum of a collection of amino acids and a dipeptide with results cross referenced against literature examples obtained with a free electron laser source. Recorded IR spectra are used for the analysis of binary mixture samples composed of constitutional isomers α-alanine and β-alanine with ratios determined to ∼4% measurement uncertainty without the aid of a front-end separation stage. This turn-key QCL-based approach is a major step in showing the viability of tag-based action spectroscopic techniques for use in future in situ planetary science sensors and general analytical applications.

Infrared Photodissociation Spectroscopy of Mass-Selected Dinuclear Transition Metal Boride Carbonyl Cluster Cations.

The transition-metal-boron bonding interactions and geometric structures of heterodinuclear transition metal carbonyl cluster cations BM(CO)n+ (M = Co, Ni, and Cu) are studied by a combination of the infrared photodissociation spectroscopy and density functional theory calculations at the B3LYP/def2-TZVP level. The BCu(CO)5+ and BCo(CO)6+ cations are characterized as an (CO)2B-M(CO)3/4+ structure involving an σ-type (OC)2B → M(CO)3,4+ dative bonding with end-on carbonyls, while for BNi(CO)5,6+ complexes with a bridged carbonyl, a 3c-2e bond involving the 5σ electrons of the bridged carbonyl and an electron-sharing bond between the B(CO)2 fragment and the Ni(CO)2,3+ subunits were revealed. Moreover, the fundamental driving force of the exclusive existence of a bridged carbonyl group in the boron-nickel complexes has been demonstrated to stem from the desire of the B and Ni centers for the favorable 8- and 18-electron structures.

Infrared Spectroscopy of [M(CO2)n]+ (M = Ca, Sr, and Ba; n = 1-4) in the Gas Phase: Solvation-Induced Electron Transfer and Activation of CO2.

Cationic complexes of heavy alkaline earth metal and carbon dioxide [M(CO2)n]+ (M = Ca, Sr, and Ba) are produced by a laser vaporization-supersonic expansion ion source in the gas phase and are studied by infrared photodissociation spectroscopy in conjunction with quantum chemistry calculations. For the n = 1 complexes, the metal-ligand binding arises primarily from the electrostatic interaction with the CO2 ligand bound to the metal (+I) center in an end-on η1-O fashion. The more highly coordinated complexes [M(CO2)n]+ with n ≥ 2 are characterized to involve a [M2+(CO2-)] core ion with the CO2- ligand bound to the metal (+II) center in a bidentate η2-O, O manner. The activation of CO2 in forming a bent CO2- moiety occurs via solvation-induced metal cation-ligand electron transfer reactions. Bonding analyses reveal that the attractive forces between M2+ and CO2- in the core cation come mainly from electrostatic attraction, but the contribution of covalent orbital interactions should not be underestimated. The atomic orbitals of metal dications that are engaged in the orbital interactions are ns and (n - 1)d orbitals.

Binding Properties of Small Electrophilic Anions [B6 X5 ]- and [B10 X9 ]- (X=Cl, Br, I): Activation of Small Molecules Based on π-Backbonding.

Superelectrophilic anions constitute a special class of molecular anions that show strong binding of weak nucleophiles despite their negative charge. In this study, the binding characteristics of smaller gaseous electrophilic anions of the types [B6 X5 ]- and [B10 X9 ]- (with X=Cl, Br, I) were computationally and experimentally investigated and compared to those of the larger analogues [B12 X11 ]- . The positive charge of vacant boron increases from [B6 X5 ]- via [B10 X9 ]- to [B12 X11 ]- , as evidenced by increasing attachment enthalpies towards typical σ-donor molecules (noble gases, H2 O). However, this behavior is reversed for σ-donor-π-acceptor molecules. [B6 Cl5 ]- binds most strongly to N2 and CO, even more strongly than to H2 O. Energy decomposition analysis confirms that the orbital interaction is responsible for this opposite trend. The extended transition state natural orbitals for chemical valence method shows that the π-backdonation order is [B6 X5 ]- >[B10 X9 ]- >[B12 X11 ]- . This predicted order explains the experimentally observed red shifts of the CO and N2 stretching fundamentals compared to those of the unbound molecules, as measured by infrared photodissociation spectroscopy. The strongest red shift is observed for [B6 Cl5 N2 ]- : 222 cm-1 . Therefore, strong activation of unreactive σ-donor-π-acceptor molecules (commonly observed for cationic transition metal complexes) is achieved with metal-free molecular anions.

Vibrational Spectroscopy and Structural Analysis of V+(C2H6)n Clusters (n = 1-4).

The vibrational structure and binding motifs of vanadium cation-ethane clusters, V+(C2H6)n, for n = 1-4 are probed using infrared photodissociation spectroscopy in the C-H stretching region (2550-3100 cm-1). Comparison of spectra to scaled harmonic frequency spectra obtained using density functional theory suggests that ethane exhibits two primary binding motifs when interacting with the vanadium cation: an end-on η2 configuration and a side-on configuration. Determining the denticity of the side on isomer is complicated by the rotational motion of ethane, implying that structural analysis based solely on Born-Oppenheimer potential energy surface minimizations is insufficient and that a more sophisticated vibrationally adiabatic approach is necessary to interpret spectra. The lower-energy side-on configuration predominates in smaller clusters, but the end-on configuration becomes important for larger clusters as it helps to maintain a roughly square-planar geometry about the central vanadium. Proximate C-H bonds exhibit elongation and large red-shifts when compared to bare ethane, particularly in the case of the side-on isomer, demonstrating initial effects of C-H bond activation, which are underestimated by scaled harmonic frequency calculations. Tagging several of the clusters with argon and nitrogen results in nontrivial effects. The high binding energy of N2 can lead to the displacement of ethane from a side-on configuration into an end-on configuration. The presence of either one or two Ar or N2 can impact the overall symmetry of the cluster, which can alter the potential energy surface for ethane rotation in the side-on isomer and may affect the accessibility of low-lying electronic excited states of V+.

Direct observation on argon tagging nitrobenzene radical anion in gas phase: Infrared photodissociation spectroscopy and theoretical calculation.

The infrared photodissociation spectroscopy was applied to characterize nitrobenzene radical anion (NB-). NB- tagged by argon [NB(Ar)-] was prepared by a mixture of nitrobenzene/Ar through a supersonic ion source and then selected by a time-of-flight mass spectrometer. Eight strong peaks observed at 977.9, 999.6, 1059.8, 1275.7, 1309.7, 1339.7, 1367.6 and 1581.7cm-1 in the fingerprint region were assigned to NB(Ar)-, corresponding to CC bending, CC stretching, CC bending+symmetric O-N stretching vibration, antisymmetric O-N and CC stretching vibration, antisymmetric O-N stretching and CH rocking vibration, CC stretching+antisymmetric O-N stretching vibration, C-N stretching vibration, and symmetric CC stretching vibration. Most interestingly, the distinguishable CH stretching vibrations were observed at 3006.5, 3048.6 and 3084.5cm-1 absorptions. Combined with density functional theoretical (DFT) calculation, five tagging argon NB- isomers were optimized and analyzed with no imaginary frequency. The results indicated that most bond lengths in NB- become longer than those of neutral NB, except for the C1-C2/C4-C5 bonds, which are only slightly shorter than those of neutral NB, and the C-N bond, which is 0.085 A shorter in the anion. The NB- tagged by argon located on the nitro group had no change on bond parameters with Ar-tagging or not theoretically. Natural population analysis (NPA) show that the negative natural charges are mainly distributed on both oxygen atoms. And the one electron resonates between the nitro group and benzene ring. N-O bonds in NB- become much more polar than those of the neutral NB. This paper proved the usefulness to characterize NB(Ar)- and further explore the structures of NBn- (n>1) clusters by infrared photodissociation spectroscopy combining with the time-of-flight mass spectrometer.

Mg-Fe Bonding in the MgFe(CO)n+ (n = 4-9) Cation Complexes: An Infrared Photodissociation Spectroscopic and Theoretical Study.

Heteronuclear magnesium-iron carbonyl cation complexes MgFe(CO)n+ (n = 4-9) are prepared in the gas phase and are detected by mass-selected infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The geometric structures and the metal-metal bonding are discussed with the aid of quantum chemical calculations. The MgFe(CO)9+ cation is a coordinatively saturated complex. Each complex is characterized to contain more than one isomer. The small complexes (n = 4-6) possess the Mg-Fe bonded [(OC)n-4Mg-Fe(CO)4]+ and/or [(OC)n-5Mg-Fe(CO)5]+ structures with all the carbonyl ligands terminally bonded. For the larger complexes with n = 7-9, the [(OC)n-4Mg-Fe(CO)4]+ structure is the major isomer experimentally observed. In addition, the [(OC)n-5Mg-OC-Fe(CO)4]+ isomer involving a linear bridging carbonyl ligand is also characterized. Bonding analyses indicate that each [(OC)n-4Mg-Fe(CO)4]+ complex contains a Mg-Fe electron-sharing σ bond. The metal-metal bond is described as a Mg(+I)-Fe(0) bond in MgFe(CO)4+ and as a Mg(+II)-Fe(-I) bond in the larger n = 5-9 complexes.

K+-Selectivity Due to Coordination with a D4d-Symmetric Homochiral Proline Octamer Verified by Mass Spectrometry and Infrared Photodissociation Spectroscopy.

Both phenomena of homochirality and sodium-potassium ion selectivity in cells have been regarded as important issues in the process of the origin of life. However, whether K+/Na+ selectivity was involved in homochirogenesis has never been considered. Herein, we report that a homochiral proline octamer shows high K+-selectivity. Coordination of K+ results in formation of a stable, noncovalent, D4d-symmetric complex, as demonstrated by mass spectrometry, infrared photodissociation spectroscopy, and calculations. A cooperative relationship between an eight-coordinated metal cation and a homochirality-restricted topological hydrogen-bonded proline network is the key for the K+/Na+ selectivity. As the complex comprises merely the basic chiral amino acid, it provides a possible linkage between K+/Na+ selectivity and the origin of chirality on the prebiotic Earth.

Hydrogen Bonding Effect on the Oxygen Binding and Activation in Cobalt(III)-Peroxo Complexes.

Cobalt(III)peroxo complexes serve as model metal complexes mediating oxygen activation. We report a systematic study of the effect of hydrogen bonding on the O2 binding energy and the O-O bond activation within the cobalt(III)peroxo complexes. To this end, we prepared a series of tris(pyridin-2-ylmethyl)amine-based cobalt(III)peroxo complexes having either none, one, two, or three amino groups in the secondary coordination sphere. The hydrogen bonding between the amino group(s) and the peroxo ligand was investigated within the isolated complexes in the gas phase using helium tagging infrared photodissociation spectroscopy, energy-resolved collision-induced dissociation experiments, and density functional theory. The results show that the hydrogen bonding stabilizes the cobalt(III)peroxo core, but the effect is only 10-20 kJ mol-1. Introducing the first amino group to the secondary coordination sphere has the largest stabilization effect; more amino groups do not change the results significantly. The amino group can transfer a hydrogen atom to the peroxo ligands, which results in the O-O bond cleavage. This process is thermodynamically favored over the O2 elimination but entropically disfavored.

Spectroscopic characterization of heteronuclear iron-chromium carbonyl cluster anions.

Infrared photodissociation spectroscopy has been used to investigate CrFe(CO)n- (n = 4-9) clusters in the gas phase. Comparison of the observed spectra in the carbonyl stretching frequency region with those predicted for low-lying isomers by DFT calculations showed that the observed CrFe(CO)n- (n = 4-8) clusters could be characterized to have Cr-Fe bonded (OC)4Fe-Cr(CO)n-4 structures. The coexistence of isomers with the (OC)Fe-Cr(CO)5 and (OC)3Fe-Cr(CO)4 structures was also observed for CrFe(CO)6- and CrFe(CO)7- anions, respectively. The CrFe(CO)n- (n = 4-8) complexes were strongly bonded systems. The CrFe(CO)8- complex was a coordination-saturated cluster, and the CrFe(CO)9- anion was characterized to contain a CrFe(CO)8- core tagged by one CO molecule. Bonding analysis revealed that the Cr-Fe bonds in the CrFe(CO)n- (n = 4-8) clusters were predominantly σ-type single bonds. The iron center in the Fe(CO)4 moiety and the chromium center in the Cr(CO)5 moiety fulfilled the 18-electron configuration for the CrFe(CO)n- (n = 4-6) clusters. As in the CrFe(CO)n- (n = 7, 8) complexes, the iron center in the Fe(CO)4 moiety exhibited a 17-electron configuration, while the chromium center in the Cr(CO)4 moiety exhibited a 16-electron configuration. These findings provide valuable insights into the structure and bonding mechanism of heterometallic carbonyl clusters.

Selective confinement of potassium, rubidium, or caesium ions in a non-covalent hydroxyproline octamer cage stabilized by cis-hydroxyl locks.

While numerous studies have focused on the impact of chirality on some magic amino acid clusters, this article investigates the effects of steric isomerization using 4-hydroxyproline octamers as a model system. Through mass spectrometry, infrared photodissociation spectroscopy, and theoretical calculation, it was demonstrated that the cis-4-hydroxy-L-proline octamer can selectively cage potassium, rubidium, or caesium ions through stable cis-hydroxyl locks, while the trans-form cannot. The results highlight the importance of hydroxyl group orientation in designing biocompatible membrane transporters with high ion-selectivity.

Mg(I)-Fe(-II) and Mg(0)-Mg(I) covalent bonding in the MgnFe(CO)4- (n = 1, 2) anion complexes: an infrared photodissociation spectroscopic and theoretical study.

Heteronuclear magnesium-iron carbonyl anion complexes MgFe(CO)4- and Mg2Fe(CO)4- are produced in the gas phase and are detected by mass-selected infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The geometric structures and the metal-metal bonding are discussed with the aid of quantum chemical calculations. Both complexes are characterized to have a doublet electronic ground state with C3v symmetry containing a Mg-Fe bond or a Mg-Mg-Fe bonding unit. Bonding analyses indicate that each complex involves an electron-sharing Mg(I)-Fe(-II) σ bond. The Mg2Fe(CO)4- complex involves a relatively weak covalent Mg(0)-Mg(I) σ bond.

Infrared spectrum of the 1-cyanoadamantane cation: evidence of hydrogen transfer and cage-opening upon ionization.

The radical cations of diamondoids are important intermediates in their functionalization reactions and are also candidates as carriers for astronomical absorption and emission features. Although neutral diamondoids have been studied extensively, information regarding their radical cations is largely lacking, particularly for functionalized diamondoid derivatives. Herein, we characterize the structure of the 1-cyanoadamantane radical cation (C10H15CN+, AdCN+) using infrared photodissociation (IRPD) spectroscopy of mass selected AdCN+N2 clusters in the XH stretch range (2400-3500 cm-1) and dispersion-corrected density functional theory calculations (B3LYP-D3BJ/cc-pVTZ). A group of three distinct CH stretch bands are observed in the 2800-3000 cm-1 range, in addition to a highly redshifted absorption at 2580 cm-1 attributed to the acidic CH proton predicted by calculations. An unexpected broad absorption peaking at 3320 cm-1 is also detected and assigned to an NH stretch mode based on its width and frequency. Calculations indicate that hydrogen atom transfer (HAT) from the adamantyl cage (C10H15, Ady) to the N atom of the CN group yields lower energy structures, with an open-cage isomer exhibiting such hydrogen transfer being the global minimum on the potential energy surface. The energy barriers involved in the formation of this open-cage isomer are also lower than those calculated for generation of the analogous open-cage 1-amantadine cation isomer which has previously been identified by IRPD. The combined consideration of IRPD spectra and calculations indicates a major population of the nascent canonical closed-cage isomer and a smaller population of the global minimum isomer featuring both cage-opening and hydrogen transfer.

Infrared photodissociation spectroscopy of mass-selected [TaO3(CO2)n]+ (n = 2-5) complexes in the gas phase.

We report a joint experimental and theoretical study on the structures of gas-phase [TaO3(CO2)n]+ (n = 2-5) ion-molecule complexes. Infrared photodissociation spectra of mass-selected [TaO3(CO2)n]+ complexes were recorded in the frequency region from 2200 to 2450 cm-1 and assigned through comparing with the simulated infrared spectra of energetically low-lying structures derived from quantum chemical calculations. With the increasing number of attached CO2 molecules, the larger clusters show significantly enhanced fragmentation efficiency and a strong band appears at around 2350 cm-1 near the free CO2 antisymmetric stretching vibration band, indicating only a small perturbation of CO2 molecules on the secondary solvation sphere while higher frequency bands corresponding to the core structure remain largely unaffected. A core structure [TaO3(CO2)3]+ is identified to which subsequent CO2 ligands are weakly attached and the most favorable cluster growth path is verified to proceed on the triplet potential energy surface higher in energy than that of ground states. Theoretical exploration reveals a two-state reactivity (TSR) scenario in which the energetically favored triplet transition state crosses over the singlet ground state to form a TaO3+ core ion, providing new information on the cluster formation correlated with the reactivity of tantalum metal oxides towards CO2.

Carbon dioxide activation by discandium dioxide cations in the gas phase: a combined investigation of infrared photodissociation spectroscopy and DFT calculations.

We present a combined computational and experimental study of CO2 activation at the Sc2O2+ metal oxide ion center in the gas phase. Density functional theory calculations on the structures of [Sc2O2(CO2)n]+ (n = 1-4) ion-molecule complexes reveal a typical end-on binding motif as well as bidentate and tridentate carbonate-containing configurations. As the number of attached CO2 molecules increases, activated forms tend to dominate the isomeric populations. Distortion energies are unveiled to account for the conversion barriers from molecularly bound isomers to carbonate structures, and show a monotonically decreasing trend with successive CO2 ligand addition. The infrared photodissociation spectra of target ion-molecule complexes were recorded in the 2100-2500 cm-1 frequency region and interpreted by comparison with simulated IR spectra of low-lying isomers representing distinct configurations, demonstrating a high possibility of carbonate structure formation in current experiments.

Coordination and Spin States in Fe+(C2H2)n Complexes Studied with Selected-Ion Infrared Spectroscopy.

Fe+(acetylene)n ion-molecule complexes are produced in a supersonic molecular beam with pulsed laser vaporization. These ions are mass selected and studied with infrared photodissociation spectroscopy in the C-H stretching region, complemented by computational chemistry calculations. All C-H stretch vibrations are shifted to frequencies lower than the vibrations of isolated acetylene because of the charge transfer that occurs between the metal ion and the molecules. Complexes in the size range of n = 1-4 are found to have structures with individual acetylene molecules bound to the core metal ion via cation-π interactions. The coordination is completed with four ligands in a structure close to a distorted tetrahedron. Larger complexes in the range of n = 5-8 have external acetylene molecules solvating this n = 4 core ion via CH-π bonding to inner-shell ligands. DFT computations predict that quartet spin states are more stable for all complex sizes, but infrared spectra for quartet and doublet spin states are quite similar, precluding definitive determination of the spin states. There is no evidence for any of these complexes having acetylenes coupled into reacted structures. This is consistent with computed thermochemistry, which finds significant activation barriers to such reactions.

Host‐guest tuning of the CO2 reduction activity of an iron porphyrin cage

AbstractEfficient electrocatalytic CO2 reduction requires developing catalysts with high selectivities and high activities, which is simultaneously difficult to achieve. Here, we present a new approach to tune the CO2 reduction activity based on host‐guest chemistry enabled by an iron porphyrin cage catalyst. The cage design allows the hosting of alkali metals in the side walls causing a change in the electrostatic potential inside the cage cavity. Density functional theory calculations show that the guest potassium ions assist the reduction of CO2 by inverting the two‐electron transfer from iron(0) to CO2 from endothermic to exothermic. Accordingly, electrochemical experiments with the cage catalyst show that in the presence of the potassium ions, the overpotential for the CO2 reduction decreases, and the catalytic activity increases while the high selectivity of the cage is retained. A novel coupling between the electrochemical cell and a mass spectrometer allowed the trapping of the key intermediates. Cryogenic ion spectroscopy characterization of the intermediates showed the details of the potassium ions hosting in the reduced cage and of the stabilization of the Fe‐COOH intermediates by the interaction with the potassium ions at the single‐molecule level.Key points Host‐guest chemistry of iron porphyrin‐cage catalysts in electrocatalytic CO2 reduction results in an increase in the activity and the selectivity of the catalysis. Electrochemistry—mass spectrometry coupling allowed studying of the reaction intermediates in CO2 reduction by mass spectrometry and by helium tagging infrared photodissociation spectroscopy. DFT calculations showed the details of the CO2 reduction pathway inside of the cage cavity and the working principles of the reactivity enhancement by the host‐guest chemistry.

Cis- and trans-binding influences in [NUO·(N2)n

Uranium nitride-oxide cations [NUO]+ and their complexes with equatorial N2 ligands, [NUO·(N2)n]+ (n = 1-7), were synthesized in the gas phase. Mass-selected infrared photodissociation spectroscopy and quantum chemical calculations confirm [NUO·(N2)5]+ to be a sterically fully coordinated cation, with electronic singlet ground state of 1A1, linear [NUO]+ core, and C5v structure. The presence of short N-U bond distances and high stretching modes, with slightly elongated U-O bond distances and lowered stretching modes, is rationalized by attributing them to cooperative covalent and dative [ǀN≡U≡Oǀ]+ triple bonds. The mutual trans-interaction through flexible electronic U-5f6d7sp valence shell and the linearly increasing perturbation with increase in the number of equatorial dative N2 ligands has also been explained, highlighting the bonding characteristics and distinct features of uranium chemistry.